(η5‐Cyclopentadienyl)[(1,2,3,4,4a,10a‐η)‐1‐methylthianthrene]iron(II) hexafluoridophosphate acetone 0.33‐solvate

The title complex salt, [Fe(C₅H₅)(C₁₃H₁₀S₂)]PF₆·0.33C₃H₆O, obtained from an acetone–diethyl ether–dichloromethane mixture at 280 (2) K, has three cationic molecules (A–C), three hexafluoridophosphate counter‐anions and one acetone solvent molecule in the asymmetric unit. Two of the three cations contain FeCp (Cp is cyclopentadienyl) inside the fold of the heterocycle. The dihedral angles between the planes of the external (complexed and uncomplexed) benzene rings in the thianthrene molecule are 146.5 (2)° for FeCp‐out‐of‐fold molecule A, and 139.0 (3) and 142.5 (2)° for the two FeCp‐in‐fold molecules B and C, respectively. The complexed Cp and benzene rings in each molecule are almost parallel, with a dihedral angle between the planes of 0.2 (5)° for molecule A, 2.8 (5)° for B, and 2.19 (4) and 6.86 (6)° for the disordered Cp ring in C.     

Bildung und Kristallstruktur von FcCH(t‐Bu)NHCH(Me)CH2OMe · LiI · Et2O

Formation and Crystal Structure of FcCH( t ‐Bu)NHCH(Me)CH₂OMe · LiI · Et₂O The title compound FcCH(t‐Bu)NHCH(Me)CH₂OMe · LiI · Et₂O ( 1 · LiI · Et₂O) was obtained by reaction of FcCH(t‐Bu)N(Li)CH(Me)CH₂OMe with MeI in a molar ratio 1 : 1 in diethylether. The Li atom is substituted by an H atom yielding the secondary amine. The formation of the expected N‐methyl substituted species could not be observed. 1 creates monomeric molecules with four coordinate Li atoms as a result of Li–N and Li–O interactions of the corresponding atoms of the ferrocenyl ligand and a solvent molecule. 1 · LiI · Et₂O: Space group P2₁2₁2₁, Z = 4, lattice dimensions at –60 °C: a = 10.492(2), b = 13.225(2), c = 18.846(3) Å, β = 90°, R₁ = 0.0478, wR₂ = 0.0801.     

Difluorotetrakis(2‐oxypyridine)dirhenium(III) – Preparation,Crystallographic Structure,and Electrochemical Properties

The solid‐state‐melt reaction of (NH₄)₂[Re₂F₈] · 2H₂O with 2‐hydroxypyridine (2‐HOpy) produced dark‐red Re₂(2‐Opy)₄F₂ ( 1 ). This air‐stable compound was obtained in crystalline form as 1· CHCl₃. It was characterized in the solid state by single‐crystal X‐ray diffraction and in solution by UV/Vis spectroscopy and cyclic voltammetry. 1· CHCl₃ forms triclinic crystals with α = 8.3254(5) Å, b = 8.5563(5) Å, c = 11.6784(8) Å, α = 82.723(3)°, β = 75.769(3) °, γ = 64.407(2) °. The Re–Re and Re–F distances were 2.2091(7) and 2.115(6) Å, respectively. The molecule is isostructural with the corresponding chloro derivative.     

(Ph4P)2[Be3(μ‐OH)3(H2O)6]Cl5: Kristallstruktur und DFT‐Rechnungen

Bis(tetraphenylphosphonium)‐tris(μ‐hydroxo)hexaaquatriberylliumpentachloride, (Ph₄P)₂[Be₃(μ‐OH)₃(H₂O)₆]Cl₅ ( 1 ), was surprisingly obtained by reaction of (Ph₄P)N₃ · n H₂O with BeCl₂ in dichloromethane suspension and subsequent crystallization from acetonitrile to give single crystals of composition 1· 5.25CH₃CN. According to the crystal structure determination space group P , Z = 2, lattice dimensions at 100 K: a = 1354.8(2), b = 1708.7(2), c = 1753.2(2) pm, α = 114.28(1)°, β = 94.80(1)°, γ = 104.51(1)°, R₁ = 0.0586] the [Be₃(μ‐OH)₃(H₂O)₆]³⁺ cations form six‐mem‐bered Be₃O₃ rings with boat conformation and distorted tetrahedrally coordinated beryllium atoms with the terminally coordinated H₂O molecules. The structure ist characterized by a complicated three dimensional hydrogen‐bridging network including O–H ··· O, O–H ··· Cl, and O–H ··· NCCH₃ contacts. DFT calculations result in nearly planar [Be₃(OH)₃] six‐membered ring conformations.     

Syntheses and Structures of Two Selenite Chloride Hydrates: Co(HSeO3)Cl · 3 H2O and Cu(HSeO3)Cl · 2 H2O

The first selenite chloride hydrates, Co(HSeO₃)Cl · 3 H₂O and Cu(HSeO₃)Cl · 2 H₂O, have been prepared from solution and characterised by single‐crystal X‐ray diffraction. The cobalt phase adopts an unusual “one‐dimensional” structure built up from vertex‐sharing pyramidal [HSeO₃]^2–, and octahedral [CoO₂(H₂O)₄]^2– and [CoO₂(H₂O)₂Cl₂]^4– units. Inter‐chain bonding is by way of hydrogen bonds or van der Waals' interactions. The atomic arrangement of the copper phase involves [HSeO₃]^2– pyramids and Jahn‐Teller distorted [CuCl₂(H₂O)₄] and [CuO₄Cl₂]^8– octahedra, sharing vertices by way of Cu–O–Se and Cu–Cl–Cu bonds. Crystal data: Co(HSeO₃)Cl · 3 H₂O, M_r = 276.40, triclinic, space group P 1 (No. 2), a = 7.1657(5) Å, b = 7.3714(5) Å, c = 7.7064(5) Å, α = 64.934(1)°, β = 68.894(1)°, γ = 71.795(1)°, V = 337.78(7) ų, Z = 2, R(F) = 0.036, wR(F) = 0.049. Cu(HSeO₃)Cl · 2 H₂O, M_r = 263.00, orthorhombic, space group Pnma (No. 62), a = 9.1488(3) Å, b = 17.8351(7) Å, c = 7.2293(3) Å, V = 1179.6(2) ų, Z = 8, R(F) = 0.021, wR(F) = 0.024.     

Molecular and Low‐dimensional Coordination Compounds of Copper(II) and 3, 5‐Dimethylpyrazole — Synthesis,Crystal Structure,and Properties

Three 3, 5‐dimethylpyrazole (pz*) copper(II) complexes, [Cu(pz*)₄(H₂O)](ClO₄)₂ ( 1 ), [Cu(pz*)₂(NCS)₂]·H₂O ( 2 ), and [Cu(pz*)₂(OOCCH=CHCOO)(H₂O)]·1.5H₂O ( 3 ), have been synthesized and characterized with single crystal X‐ray structure analysis. 1 crystallizes in the tetragonal space group, 14/m, with a = 14.027 (3) Å, c = 16.301 (5) Å, and Z = 4. 2 crystallizes in the monoclinic space group, P2₁/c, with a = 8.008 (3) Å, b = 27.139 (9) Å, c = 8.934 (3) Å, β = 106.345 (6)°, and Z = 4. 3 crystallizes in the triclinic space group, P1¯, with a = 7.291 (9) Å, b = 10.891 (13) Å, c = 11.822 (14) Å, α = 80.90 (2)°, β = 79.73(2)°, γ = 70.60(2)°, and Z = 2. In 1 , one water molecule and four pz* ligands are coordinated to Cu^II. Two [Cu(pz*)₄(H₂O)]²⁺ units are connected to ClO₄^— via hydrogen bonds. One lattice water molecule is found in the unit cell of 2 , which forms an one‐dimensional chain via intermolecular hydrogen bonds with the N‐H atom of pz*. In 3 , the oxygen atom of the coordinated water molecule is connected with two C=O groups of two neighbouring maleic acid molecules to form a linear parallelogram structure. Another C=O group of maleic acid forms a hydrogen bond with the N‐H atom of pz* to create a two‐dimensional structure. The spectroscopic and bond properties are also discussed.     

3,4,6‐Tri‐O‐acetyl‐1,2‐O‐[1‐(exo‐ethoxy)ethylidene]‐β‐d‐mannopyranose 0.11‐hydrate

The title compound, C₁₆H₂₄O₁₀·0.11H₂O, is a key intermediate in the synthesis of 2‐deoxy‐2‐[¹⁸F]fluoro‐d ‐glucose (¹⁸F‐FDG), which is the most widely used molecular‐imaging probe for positron emission tomography (PET). The crystal structure has two independent molecules (A and B) in the asymmetric unit, with closely comparable geometries. The pyranose ring adopts a ⁴C₁ conformation [Cremer–Pople puckering parameters: Q = 0.553 (2) Å, θ = 16.2 (2)° and ϕ = 290.4 (8)° for molecule A, and Q = 0.529 (2) Å, θ =15.3 (3)° and ϕ = 268.2 (9)° for molecule B], and the dioxolane ring adopts an envelope conformation. The chiral centre in the dioxolane ring, introduced during the synthesis of the compound, has an R configuration, with the ethoxy group exo to the mannopyranose ring. The asymmetric unit also contains one water molecule with a refined site‐occupancy factor of 0.222 (8), which bridges between molecules A and B via O—H...O hydrogen bonds.     

Trichloroberyllat‐Komplexe von Dimethylcyanamid,Morpholin und 4,4′‐Bipyridin

Trichloroberyllate Complexes of Dimethyl Cyanamide, Morpholine, and 4,4′‐Bipyridine The trichloroberyllate complexes (Ph₄P)[BeCl₃(NCNMe₂)] ( 1 ), (Ph₄P)[BeCl₃{HN(CH₂)₄O}] ( 2 ), and (Ph₄P)₂[(BeCl₃)₂(4,4′‐bipy)] ( 3 ) were prepared by reactions of (Ph₄P)₂[Be₂Cl₆] with dimethyl cyanamide, trimethylsilylmorpholinate, and 4,4′‐bipyridine, respectively, in dichloromethane solutions. 1 ‐ 3 were characterized by X‐ray crystallography and by IR‐spectroscopy. 1 ·CH₂Cl₂: Space group P1, Z = 1, lattice dimensions at 173 K: a = 714.2(1), b = 919.5(2), c = 1233.4(2) pm, α = 94.97(1)°, β = 90.86(1)°, γ = 111.90(1)°, R₁ = 0.0310. In the complex anion [BeCl₃(NCNMe₂)]^? the dimethyl cyanamide ligand is coordinated via a linear Be–N≡C‐NMe₂ arrangement, the CH₂Cl₂ molecules forming linear chains by hydrogen bridges ···HCH···Cl··· with the chlorine atoms of the {BeCl₃^?} groups. 2 : Space group , Z = 2, lattice dimensions at 173 K: a = 1050.9(1), b = 1099.7(1), c = 1308.3(2) pm, α = 87.57(1)°, β = 70.97(1)°, γ = 74.58(1)°, R₁ = 0.0397. The complex anions are dimerized by centrosymmetric puckered eight‐membered [Be–N–H···Cl]₂ rings. 3 ·2CH₂Cl₂: Space group , Z = 2, lattice dimensions at 173 K: a = 1095.4(1), b = 1559.6(2), c = 1869.8(3) pm, α = 79.12(1)°, β = 73.83(1)°, γ = 78.76(1)°, R₁ = 0.0548. The complex contains dianions [Cl₃Be(μ‐bipy)BeCl₃]^2? with Be–N distances of 177.0(6) and 178.5(6) pm. Both {BeCl₃}^? groups form C–H···Cl hydrogen bridges with the dichloromethane molecules.     

Synthesis and Crystal Structure of [Cu2(H2O)2(phen)2(OH)2][Cu2(phen)2(OH)2(CO3)2] · 10 H2O with phen = 1,10‐phenanthroline

The blue copper complex [Cu₂(H₂O)₂(phen)₂(OH)₂][Cu₂(phen)₂(OH)₂(CO₃)₂] · 10 H₂O, which was prepared by reaction of 1,10‐phenanthroline monohydrate, CuCl₂ · 2 H₂O and Na₂CO₃ in the presence of succinic acid in CH3OH/H₂O at pH = 13.0, crystallized in the triclinic space group P1 (no. 2) with cell dimensions: a = 9.515(1) Å, b = 12.039(1) Å, c = 12.412(2) Å, α = 70.16(1)°, β = 85.45(1)°, γ = 81.85(1)°, V = 1323.2(2) ų, Z = 1. The crystal structure consists of dinuclear [Cu₂(H₂O)₂(phen)₂(OH)₂]²⁺ complex cations, dinuclear [Cu₂(phen)₂(OH)₂(CO₃)₂]^2– complex anions and hydrogen bonded H₂O molecules. In both the centrosymmetric dinuclear cation and anion, the Cu atoms are coordinated by two N atoms of one phen ligand, three O atoms of two μ‐OH groups and respectively one H₂O molecule or one CO₃^2– anion to complete distorted [CuN₂O₃] square‐pyramids with the H₂O molecule or the CO₃^2– anion at the apical position (equatorial d(Cu–O) = 1.939–1.961 Å, d(Cu–N) = 2.026–2.051 Å and axial d(Cu–O) = 2.194, 2.252 Å). Two adjacent [CuN₂O₃] square pyramids are condensed via two μ‐OH groups. Through the interionic hydrogen bonds, the dinuclear cations and anions are linked into 1D chains with parallel phen ligands on both sides. Interdigitation of phen ligands of neighboring 1D chains generated 2D layers, between which the hydrogen bonded water molecules are sandwiched.     

Hydroxo‐bridged Tetranuclear CuII Complexes: {[Cu(bpy)(OH)]4Cl2}Cl2 · 6 H2O and {[Cu(phen)(OH)]4(H2O)2}]Cl4 · 4 H2O

The blue tetranuclear Cu^II complexes {[Cu(bpy)(OH)]₄Cl₂}Cl₂ · 6 H₂O ( 1 ) and {[Cu(phen)(OH)]₄(H₂O)₂}Cl₄ · 4 H₂O ( 2 ) were synthesized and characterized by single crystal X‐ray diffraction. ( 1 ): P 1 (no. 2), a = 9.240(1) Å, b = 10.366(2) Å, c = 12.973(2) Å, α = 85.76(1)°, β = 75.94(1)°, γ = 72.94(1)°, V = 1152.2(4) ų, Z = 1; ( 2 ): P 1 (no. 2), a = 9.770(3) Å, b = 10.118(3) Å, c = 14.258(4) Å, α = 83.72(2)°, β = 70.31(1)°, γ = 70.63(1)°, V = 1252.0(9) ų, Z = 1. The building units are centrosymmetric tetranuclear {[Cu(bpy)(OH)]₄Cl₂}²⁺ and {[Cu(phen)(OH)]₄(H₂O)₂}⁴⁺ complex cations formed by condensation of four elongated square pyramids CuN₂(OH)₂L^ap with the apical ligands L^ap = Cl, H₂O, OH. The resulting [Cu₄(μ₂‐OH)₂(μ₃‐OH)₂] core has the shape of a zigzag band of three Cu₂(OH)₂ squares. The cations exhibit intramolecular and intermolecular π‐π stacking interactions and the latter form 2D layers with the non‐bonded Cl^– anions and H₂O molecules in between (bond lengths: Cu–N = 1.995–2.038 Å; Cu–O = 1.927–1.982 Å; Cu–Cl^ap = 2.563; Cu–O^ap(OH) = 2.334–2.369 Å; Cu–O^ap(H₂O) = 2.256 Å). The Cu…Cu distances of about 2.93 Å do not indicate direct interactions, but the strongly reduced magnetic moment of about 2.74 B.M. corresponds with only two unpaired electrons per formula unit of 1 (1.37 B.M./Cu) and obviously results from intramolecular spin couplings (χ_m(T‐θ) = 0.933 cm³ · mol^–1 · K with θ = –0.7 K).     

1,N6‐Etheno‐2′‐deoxytubercidin hemihydrate

The title compound [systematic name: 7‐(2‐deoxy‐β‐d ‐erythro‐pentofuranosyl)‐7H‐imidazo[1,2‐c]pyrrolo[2,3‐d]pyrimidine hemihydrate], 2C₁₃H₁₄N₄O₃·H₂O or (I)·0.5H₂O, shows two similar conformations in the asymmetric unit. These two conformers are connected through one water molecule by hydrogen bonds. The N‐glycosylic bonds of both conformers show an almost identical anti conformation with χ = −107.7 (2)° for conformer (I‐1) and −107.0 (2)° for conformer (I‐2). The sugar moiety adopts an unusual N‐type (C3′‐endo) sugar pucker for 2′‐deoxyribonucleosides, with P = 36.8 (2)° and τ_m = 40.6 (1)° for conformer (I‐1), and P = 34.5 (2)° and τ_m = 41.4 (1)° for conformer (I‐2). Both conformers and the solvent molecule participate in the formation of a three‐dimensional pattern with a `chain'‐like arrangement of the conformers. The structure is stabilized by intermolecular O—H...O and O—H...N hydrogen bonds, together with weak C—H...O contacts.     

Synthesis,Structure, and Properties of a New Calcium(II) Complex of 1,10‐Phenanthroline, 1,2,4,5‐Benzenetetracarboxylic Acid,and a New Precursor to Produce Pure Phase Micro‐crystalline Calcite Particles

The self‐assembly of 1, 0‐phenanthroline (phen) and 1,2,4,5‐benzenetetracarboxylic acid(H₄btc) with Ca(NO₃)₂ gives rise to a two‐dimensional network structure coordination polymer, [Ca(phen)(btc)_0.5(H₂O)] ( 1 ), which was characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. This compound is monoclinic, space group C2/c, with Z = 8 in a unit cell with dimensions a = 21.744(3) Å, b = 10.0151(12) Å, c = 14.7122(17) Å, β = 110.2850(10)°. The structure contains one crystallographic unique Ca^II atom, one phen coordinated molecule and a half of btc^4– anion. The phen molecule acts as a didentate ligand chelating with a Ca^II atom, whereas the btc^4– anion acts as a μ₆‐bridge linking six different Ca^II atoms to form a two‐dimensional network with (4, 4) topological structure. The three dimensional stacking structures are formed by C–H ··· O hydrogen bonding and π–π interaction. The thermal stability and fluorescent properties of 1 were investigated. Calcite particles are produced by calcination of compound 1 at 580 °C. The obtained calcite was characterized by XRD and SEM analyses.     

Zwei Tetrachlorothiotantalate: [Na‐15‐Krone‐5][TaSCl4 · Dioxan] und [Na‐15‐Krone‐5]2[(TaSCl4)2Dioxan] · S8

Two Tetrachlorothiotantalates: [Na‐15‐crown‐5][TaSCl₄ · dioxane] and [Na‐15‐crown‐5]₂[(TaSCl₄)₂dioxane] · S₈ During the reaction of Na₂S₄, TaCl₅ and 15‐crown‐5 in dichloromethane the crown ether partly suffers degradation to 1,4‐dioxane. Aside from sulfur, [Na‐15‐crown‐5][TaSCl₄ · dioxane] was the first product obtained. It crystallizes in the monoclinic space group P2₁/n with a = 1066.1, b = 1781.3, c = 1258.3 pm, β = 97.14°, Z = 4. In the [TaSCl₄ · dioxane]^– ion a dioxane molecule is loosely bonded to a square‐pyramidal TaSCl₄^– unit; two chlorine atoms are in contact with an Na⁺ ion. Upon standing with the mother liquor [Na‐15‐crown‐5]₂[(TaSCl₄)₂dioxane] · S₈ was formed. It crystallizes in the monoclinic space group C2/m; a = 1768.5, b = 1084.0, c = 1517.3 pm, β = 118.46°, Z = 4. In this case a dioxane molecule is coordinated with two TaSCl₄^– units. The [(TaSCl₄)₂ · dioxane]^2– ions and S₈ molecules alternate in the stacking direction b.     

Self‐Assembly,Spectroscopic and Electrochemical Studies of Nickel(II)‐4,8‐Diazaundecanediamide Complex

The self‐assembly of NiCl₂·6H₂O with a diaminodiamide ligand 4,8‐diazaundecanediamide (L‐2,3,2) gave a [Ni(C₉H₂₀N₄O₂)(Cl)(H₂O)] Cl·2H₂O ( 1 ). The structure of 1 was characterized by single‐crystal X‐ray diffraction analysis. Structural data for 1 indicate that the Ni(II) is coordinated to two tertiary N atoms, two O atoms, one water and one chloride in a distorted octahedral geometry. Crystal data for 1: orthorhombic, space group P 21nb, a = 9.5796(3) Å, b = 12.3463(4) Å, c = 14.6305(5) Å, Z = 4. Through NH···Cl–Ni (H···Cl 2.42 Å, N···Cl 3.24 Å, NH···Cl 158°) and OH···Cl–Ni contacts (H···Cl 2.36 Å, O···Cl 3.08 Å, OH···Cl 143°), each cationic moiety [Ni(C₉H₂₀N₄O₂) (Cl)(H₂O)]⁺ in 1 is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chainlike structure. Thermogrametric analysis of compound 1 is consistent with the crystallographic observations. The electronic absorption spectrum of Ni(L‐2,3,2)²⁺ in aqueous solution shows four absorption bands, which are assigned to the ³A_2g → ³T_2g, ³T_2g → ¹Eg, ³T_2g → ³T_1g, and ³A_2g → ³T_1g transitions of triplet‐ground state, distorted octahedral nickel(II) complex. The cyclic volammetric measurement shows that Ni²⁺ is more easily reduced than Ni(L‐2,3,2)²⁺ in aqueous solution.     

Darstellung,Kristallstruktur und IR‐Spektren von BeSeO3 · H2O – Wasserstoffbrücken und Korrelation von IR‐ und Strukturdaten in den Monohydraten MSeO3 · H2O (M = Be,Ca, Mn,Co, Ni,Zn, Cd)

Preparation, Crystal Structure and IR Spectra of BeSeO₃ · H₂O – Hydrogen Bonds and Correlation of IR and Structure Data in the Monohydrates MSeO₃ · H₂O (M = Be, Ca, Mn, Co, Ni, Zn, Cd) BeSeO₃ · H₂O (oP32) has been obtained by treating amorphous BeSeO₃ · 4 H₂O precipitated from Be(HSeO₃)₂ solutions hydrothermally at 150 °C. The crystal structure (P2₁2₁2₁, a = 560.59(4), b = 755.25(5), c = 781.14(5) pm, Z = 4, D_X = 3.092 gcm^–3, R = 0.018 for the 2034 reflections with I > 2σ_I of the enantiomer investigated) contains BeO₃(H₂O) tetrahedra built up from three selenite and one water oxygen atoms. The BeO₃(H₂O) tetrahedra are 3 D‐connected via Se atoms of trigonal pyramidal SeO₃^2– ions. The Be–O distances are 161.8 to 164.4 pm. The Se–O bond lenghts (169.2–170.3 pm) and the O–Se–O bond angles (98.1–101.4°) are normal. The water molecules of crystallization form together with the SeO₃^2– ions screw‐like hydrogen bond systems along [100]. Despite the strong synergetic effect of the Be²⁺ ions, the hydrogen bonds (d(OH…O) = 267.4 and 276.4 pm, respectively; ν_OD of matrix isolated HDO molecules: 2244 and 2405 cm^–1, respectively) are normal compared to other neutral selenite hydrates. Together with the hitherto known monohydrates M^IISeO₃ · H₂O and other beryllium salt hydrates, the hydrogen bonds of BeSeO₃ · H₂O are discussed with regard to their geometry and IR spectroscopy.     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.     

Polysulfonylamine. CLXXXIV. Kristallstrukturen molekularer Triphenylphosphangold(I)‐di(4‐X‐benzolsulfonyl)‐amide: Isomorphie und dichte Packung (X = Me,F, Cl,NO2) vs. struktursteuernde Halogenbrücken C–X···Au/O (X = Br,I)

Polysulfonylamines. CLXXXIV. Crystal Structures of Molecular Triphenylphosphanegold(I) Di(4‐X‐benzenesulfonyl)amides: Isomorphism and Close Packing (X = Me, F, Cl, NO₂) vs. Structure‐Determining C–X···Au/O Halogen Bonds (X = Br, I) In order to study the structure‐determining influence that halogen bonding can exert during the course of crystallization, solid‐state structures are compared for two previously reported and four new molecular gold(I) complexes of the type Ph₃P–Au–N(SO₂–C₆H₄–4‐X)₂, each featuring linear P,N coordination at gold and two phenyl rings with varying p‐substituents X = Me, F, Cl, NO₂, Br or I. The compounds were synthesized by reactions of Ph₃PAuX (X = Cl or I) with the corresponding silver di(arenesulfonyl)amides, crystallized from dichloromethane, and characterized by low‐temperature X‐ray diffraction. The Me, F, Cl and NO₂ congeners are isomorphic and crystallize without solvent inclusion in the chiral orthorhombic space group P2₁2₁2₁ (Z′ = 1). These structures are governed by isotropic close packing via three‐dimensional 2₁ symmetry, incidentally supported by an invariant set of C–H···O=S hydrogen bonds, CH/π interactions and π/π stackings of aromatic rings; in particular, the hard halogen atoms of the fluoro and the chloro homologues are not involved in X···Au, X···O or X···X interactions. The higher homologues, with soft halogen atoms, were obtained as a dichloromethane hemisolvate for X = Br and a corresponding monosolvate for X = I, each triclinic in the centrosymmetric space group (Z′ = 1). Here, the primary structural effect is implemented by infinite chains in which translation‐related molecules are connected for the bromo compound by a bifurcated Au···Br(2)···O=S interaction, for the iodo congener by an equivalent Au···I(2)···O=S interaction and a short halogen bond C–I(1)···O=S. The latter bond is stronger than a similar C–Br···O=S interaction and induces a conformational adjustment of the (CSO₂)₂N group from the normal twofold symmetry in the bromo compound to an energetically unfavourable asymmetric form in the iodo homologue. In both cases, pairs of antiparallel molecular catemers are associated into strands via sixfold phenyl embraces, the strands are stacked to form layers, the solvent molecules are intercalated between adjacent layers, and the crystal packings are reinforced by a number of C–H···O=S hydrogen bonds and interactions of aromatic rings.     

Synthesis and Crystal Structure of a Novel Dinuclear Copper(II) Complex, [Cu2(phen)2(H2O)2(OH)2](HCO3)2 · 6 H2O with phen = 1,10‐phenanthroline

Dark blue plate‐like crystals of [Cu₂(phen)₂ · (H₂O)₂(OH)₂](HCO₃)₂ · 6 H₂O were obtained from a CH₃OH–H₂O solution containing CuCl₂, 1,10‐phenanthroline (phen), sebacic acid and Na₂CO₃. The crystal structure (triclinic, P 1 (no. 2), a = 8.118(1), b = 9.624(1), c = 10.536(1) Å, α = 81.35(1)°, β = 88.51(1)°, γ = 75.77(1)°, Z = 1, R = 0.0332, wR² = 0.0981 for 4163 observed reflections (F ≥ 2σ(F ) out of 4595 unique reflections) consists of divalent [Cu₂(phen)₂(H₂O)₂(OH)₂]²⁺ complex cations, anionic (HCO₃)₂^2– dimers and H₂O molecules. The divalent complex cations (d(Cu…Cu) = 2.905(1) Å) are centered at inversion centers. The Cu atoms are fivefold square‐pyramidally coordinated by two nitrogen and three oxygen atoms from one bidentate chelating phen ligand, two bridging hydroxide groups and one axial water molecule (d(Cu–N)phen = 2.021(2), 2.024(2) Å; d(Cu–O)_OH = 1.941(1), 1.949(1) Å; d(Cu–O)_H2O = 2.254(2) Å). The divalent complex cations are stacked to form 2 D layers parallel (001) with 1 D π‐π stacking interactions along [100] via the terminal phen rings. The dimeric (HCO₃)₂^2– anions and the hydrogen bonded H₂O molecules are sandwiched between the 2 D layers.     

Crystal Structure of the [(C5H4BMe2)2Fe]‐4,4′‐bipyridine Polymer from High Resolution X‐Ray Powder Diffraction

The crystal structure of [(C₅H₄BMe₂)₂Fe]‐4,4′‐bipyridine [ 2 · bipy]_n has been determined by the method of simulated annealing from high resolution X‐ray powder diffraction at room temperature. The compound is of interest, because it proves that highly ordered organometallic macromolecules can be formed in the solid state via the self‐assembly of N–B‐donor‐acceptor bonds. [ 2 · bipy]_n crystallizes in the triclinic space group, P 1, Z = 2, with unit cell parameters of a = 8.3366(2) Å, b = 11.4378(3) Å, c = 12.6740(5) Å, α = 112.065(2)°, β = 108.979(1)°, γ = 90.551(2)°, and V = 1047.06(6) ų. For the structure solution of [ 2 · bipy]_n 11 degrees of freedom (3 translational, 3 orientational, 5 torsion angles) were determined within several hours, demonstrating that the crystal packing and the molecular conformation of medium sized (< 50 non‐hydrogen atoms) coordination compounds can nowadays be solved routinely from high resolution powder diffraction data.     

Supramolecular Assemblies of Mononuclear and Polymeric Nickel(II) Glutarato Complexes via π‐π Stacking Interactions and Hydrogen Bonds: [Ni(H2O)3(phen)(C5H6O4)] · H2O and [Ni(H2O)2(phen)(C5H6O4)]

Syntheses of the sky blue complex compounds [Ni(H₂O)₃(phen)(C₅H₆O₄)] · H₂O ( 1 ) and [Ni(H₂O)₂(phen)(C₅H₆O₄)] ( 2 ) were carried out by the reactions of 1,10‐phenanthroline monohydrate, glutaric acid, NiSO₄ · 6 H₂O and Na₂CO₃ in CH₃OH/H₂O at pH = 6.9 and 7.5, respectively. The crystal structure of 1 (P 1 (no. 2), a = 14.289 Å, b = 15.182 Å, c = 15.913 Å, α = 67.108°, β = 87.27°, γ = 68.216°, V = 2934.2 ų, Z = 2) consists of hydrogen bonded [Ni(H₂O)₃‐ (phen)(C₅H₆O₄)]₂ dimers and H₂O molecules. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, three water O atoms and one carboxyl O atom from one monodentate glutarato ligand (d(Ni–N) = 2.086, 2.090 Å; d(Ni–O) = 2.064–2.079 Å). Through the π‐π stacking interactions and intermolecular hydrogen bonds, the dimers are assembled to form 2 D layers parallel to (0 1 1). The crystal structure of 2 (P2₁/n (no. 14), a = 7.574 Å, b = 11.938 Å, c = 18.817 Å, β = 98.48°, V = 1682.8 ų, Z = 4) contains [Ni(H₂O)₂(phen)(C₅H₆O₄)_2/2] supramolecular chains extending along [010]. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, two water O atoms and two carboxyl O atoms from different bis‐monodentate glutarato ligands with d(Ni–N) = 2.082, 2.105 Å and d(Ni–O) = 2.059–2.087 Å. The supramolecular chains are assembled into a 3 D network by π‐π stacking interactions and interchain hydrogen bonds. A TG/DTA of 2 shows two endothermic effects at 132 °C and 390 °C corresponding to the complete dehydration and the lost of phen.